面向C4烯烃混合物吸附分离的真实金属-有机骨架材料高通量筛选

doi:10.6023/A20110526

摘要/Abstract

常规的烯烃/烷烃冷冻加压精馏分离过程具有高能耗和低效率的特点, 吸附分离技术可以在温和条件下高效纯化烯烃分子而在烯烃/烷烃分离领域展现出广阔应用前景. 本工作采用高通量筛选技术从12723个真实金属-有机骨架(MOF)材料中筛选具有优异C4烯烃混合物选择性吸附性能的吸附剂, 用于1,3-丁二烯的分离纯化. 首先, 根据MOF材料的结构参数进行筛选获得了7681个具有合适孔径和比表面积的吸附剂. 然后, 采用分子力学方法计算出上述吸附剂的力学性能, 以UIO-66力学性能为阈值得到959个结构稳定的候选MOF材料. 接下来采用巨正则蒙特卡洛(GCMC)方法模拟出298 K、0.1 MPa下五元等摩尔C4烯烃混合物在不同候选MOFs中的选择性吸附行为, 根据候选MOFs对1,3-丁二烯的吸附性能分值(APS)进行排序, 得到具有最佳吸附分离性能的8种MOF材料. 通过定量构效关系、吸附等温线及理想吸附溶液理论等揭示了高吸附分离性能MOFs的结构特征, 利用穿透曲线模拟进一步验证了填充最优吸附剂RIGPEE01的固定床能够有效分离2-顺式丁烯/1,3-丁二烯双组分混合物. 最后, 通过径向分布函数和结合能计算分析, 确定RIGPEE01对1,3-丁二烯产生优先吸附的机理主要归因于Cu(I)强吸附位点、π键耦合效应和尺寸筛分效应. 本工作提出的高通量筛选方法以及从分子尺度理解MOF材料应用于烯烃分离机制的视角, 为进一步开发烯烃/烷烃混合物分离的新型吸附剂奠定了理论基础.

关键词: 真实金属-有机骨架材料, 分子模拟, 高通量筛选, 吸附分离, 1,3-丁二烯

The conventional separation process of olefin/paraffin with cryogenic and high-pressure distillation usually exhibits high energy consumption and low efficiency. The adsorption separation technology is widely promising in the field of olefin/paraffin separation because of its mild operation conditions and high energy efficiency. In this work, high-throughput screening was adopted to find the optimal adsorbents from 12723 real metal-organic framework (MOF) materials, which is available for adsorption separation of 1,3-butadiene from C4 olefin/paraffin mixture. Firstly, 7681 adsorbents with suitable pore size and specific surface area were selected from the total database according to their structural parameters. Then their mechanical properties were computed by molecular mechanics. The mechanical properties of UIO-66 were used as the threshold to obtain 959 candidate MOFs with stable structure. Secondly, the grand canonical Monte Carlo (GCMC) simulation was performed to calculate the selective adsorption behavior of a quinary equimolar C4 olefin mixture in different candidate MOFs at 298 K and 0.1 MPa. According to their adsorption performance scores (APS) of 1,3-butadiene, the candidate MOFs are ranked to obtain 8 MOFs with the optimal adsorption and separation performance. The structural characteristics of MOFs with high adsorption and separation performance are revealed through quantitative structure-activity relationship, adsorption isotherm and ideal adsorption solution theory. The breakthrough curve simulation further verified that 2-cis-butene could effectively separate from 1,3-butadiene in the fixed bed filled with the optimal adsorbent RIGPEE01. Finally, it is determined that the preferential adsorption mechanism of 1,3-butadiene in RIGPEE01 is mainly due to the strong adsorption sites of Cu(I), π bond coupling effect and the size sieving effect based on the radial distribution function and binding energy analysis. The high-throughput screening method and the molecule-level insights on the olefin separation mechanism of MOFs proposed in this work have laid a theoretical foundation for the further development of new adsorbents for the separation of olefin/paraffin mixtures.

Key words: real metal-organic framework, molecular simulation, high-throughput screening, adsorption separation, 1,3-butadiene

引用此文

杨磊, 吴宇静, 吴选军, 蔡卫权. 面向C4烯烃混合物吸附分离的真实金属-有机骨架材料高通量筛选[J]. 化学学报, 2021, 79(4): 520-529.

Lei Yang, Yujing Wu, Xuanjun Wu, Weiquan Cai. High-throughput Screening of Real Metal-organic Frameworks for Adsorption Separation of C4 Olefins[J]. Acta Chimica Sinica, 2021, 79(4): 520-529.

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图/表 11

Atom type	(ε/k_B)/K	σ/nm	Atom type	(ε/k_B)/K	σ/nm	Atom type	(ε/k_B)/K	σ/nm
C	52.84	0.343	Cu	2.516	0.311	Cd	114.73	0.254
H	22.14	0.257	Zn	62.40	0.246	Ag	18.12	0.280
O	30.19	0.312	Co	7.05	0.256	Ni	7.55	0.252
N	34.72	0.326	Mn	6.54	0.264	Fe	6.54	0.259

表1. 部分MOFs的Lennard-Jones参数

Table 1. Lennard-Jones parameters of partial MOFs

图1. 12723个CoRE-MOF材料不同结构描述符的主成分分析

Figure 1. PCA on various structural descriptors of 12723 CoRE-MOFs

图2. CoRE-MOF材料筛选流程示意

Figure 2. Flowsheet diagram for computational screening of CoRE-MOFs

图3. 298 K、100 kPa下1,3-丁二烯在400个随机挑选的MOF材料中(a), (b)吸附量和(c), (d)选择性分别与LCD和VSA之间关系

Figure 3. Relationship plots of (a), (b) NBD and (c), (d) SBD versus LCD and VSA, respectively, for adsorption of 1,3-butadiene in 400 random MOFs at 298 K and 100 kPa.

MOFs	N_BD/ (mol•kg^–1)	S_BD	APS	LCD/nm	PLD/nm	VSA/ (m²•cm^–3)	Φ	OMS	Linker^a	Q⁰_st,BD/ (kJ•mol^–1)
RIGPEE01	1.90	13.9	26.4	0.433	0.345	566	0.462	Cu	L6	45.26
RIGPEE	1.86	11.5	20.9	0.437	0.350	598	0.468	Cu	L6	50.84
ETIPII	2.28	6.57	15.0	0.441	0.363	795	0.523	Zn	L1, L2	71.60
MORFEG	1.53	8.06	12.3	0.480	0.349	714	0.471	Cu	L5	43.19
IWELIG01	1.35	7.80	10.6	0.469	0.450	512	0.399	none	L4	46.75
YUSGID	1.04	9.96	10.3	0.450	0.372	753	0.425	none	L8, L9	55.54
CUVTIX	1.78	5.77	10.3	0.671	0.342	1159	0.506	none	L7	37.40
FITHIA	1.29	7.76	10.0	0.436	0.385	941	0.431	Sc	L3	55.70

表2. 前8个高吸附性能材料以及它们的结构性质

Table 2. Top 8 MOFs with high APS and their physical properties

图4. 1140个MOF材料 (a), (b) 体积模量; (c), (d) 剪切模量分别与 LCD和VSA之间的关系

Figure 4. Relationship plots of (a), (b) bulk modulus; (c), (d) shear modulus versus LCD and VSA, respectively, for 1140 MOFs.

图5. 298 K、100 kPa下1,3-丁二烯在959个候选MOF材料中的吸附量对(a) LCD; (b) VSA之间散点图和对(c) LCD; (d) VSA之间的箱图

Figure 5. Scatter plots and box plots of NBD versus (a), (c) LCD; (b), (d) VSA. NBD refers to adsorption capacity of 1,3-butadiene in 959 candidate MOFs at 298 K and 100 kPa.

图6. 298 K、100 kPa下1,3-丁二烯在959个候选MOF材料中吸附量和选择性之间的关系散点图.

Figure 6. Relationship plots of SBD versus NBD for 1,3-butadiene adsorption in 959 candidate MOFs at 298 K and 100 kPa. All points are colored by adsorption performance score (APS) of 1,3-butadiene.

图7. 在298 K下、RIGPEE01中, (a) 不同C4烯烃纯组分吸附等温线; (b)五元C4烯烃等摩尔混合组分吸附等温线; 1,3-丁二烯/2-顺式丁烯二元等摩尔混合组分(c)吸附等温线; (d) 0.1 MPa下固定床穿透曲线.

Figure 7. At 298 K and in RIGPEE01, (a) adsorption isotherms of various pure C4 olefins; (b) adsorption isotherms of quinary equimolar mixture; 1,3-butadiene/2-cis-butene binary equimolar mixture (c) adsorption isotherms; (d) breakthrough curves in fixed column at 0.1 MPa.

图8. 298 K、0.1 MPa下, RIGPEE01不同骨架原子与1,3-丁二烯相互作用原子对的径向分布函数.

Figure 8. Radial distribution functions of interaction atom pairs between various framework atoms of RIGPEE01 and 1,3-butadiene at 298 K and 0.1 MPa.

图9. (a) 分子模拟的1,3-丁二烯在RIGPEE01中吸附平衡构象, 浅蓝色圆球: 联合碳原子; 粉色、灰色及蓝色线分别代表RIGPEE01中的Cu、C和N原子; 密度泛函理论优化RIGPEE01中(b) 1,3-丁二烯; (c) 1-丁烯; (d) 2-顺式丁烯; (e) 2-反式丁烯; (f) 异丁烯分子吸附构象与结合能. 绿色球为客体C原子, 灰、蓝和粉色球分别为RIGPEE01材料C、N和Cu原子. 为清晰可见, 将客体H原子省去. 结合能E和原子间距离的单位分别为kJ•mol–1和nm.

Figure 9. (a) Equilibrium configuration of 1,3-butadiene adsorbed in RIGPEE01 under molecular simulation, ice blue spheres refer to united carbon atoms of 1,3-butadiene; pink, grey and blue lines refer to Cu, C and N atoms, respectively; equilibrium configuration and binding energy of (b) 1,3-butadiene; (c) 1-butene; (d) 2-cis-butene; (e) 2-trans-butene; (f) isobutene adsorbed in RIGPEE01, calculating by density functional theory for geometrical optimization. Green sphere refers to carbon in guest molecule. Grey, blue and pink spheres refer to C, N and Cu atoms, respectively, in RIGPEE01. H atoms in guest molecule are omitted for clarity. The unit of binding energy E and distance of atom pairs are kJ•mol–1 and nm, respectively.

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